Carbamates containing an oxime ether function

ABSTRACT

THE INVENTION RELATES TO NEW OXIME ETHERS OF THE FORMULA   1-((4-(R1-NH-COO-),3,5-DI(X-)PHENYL)-CH=N-O-),2-(O2N-),   R3-BENZENE   WHEREIN R1, R2, R3 AND X HAVE THE MEANSINGS GIVEN BELOW SAID OXIME ETHERS ARE USED IN HERBICIDAL PREPARATIONS FOR CONTROLLING UNDESIRED PLANT GROWTH IN CULTURES OF CEREALS, MAIZE, RICE AND SOYA. SOME OF THESE ETHERS CAN ALSO BE USED FOR COMBATTING PESTS OF THE ORDER ACERINAE.

United States Patent M 3,772,385 CARBAMATES CONTAINING AN OXIME ETHER FUNCTION Adolf Hubele, Riehen, near Basel, Switzerland, assignor to Ciba-Geigy AG, Basel, Switzerland No Drawing. Continuation-impart of abandoned application Ser. No. 786,762, Dec. 24, 1968. This application Nov. 4, 1971, Ser. No. 195,822

Int. Cl. C07c 131/12 U.S. Cl. 260-472 V 13 Claims ABSTRACT OF THE DISCLOSURE The invention relates to new oxime ethers of the formula wherein R R R and X have the meanings given below, Said oxime others are used in herbicidal preparations for controlling undesired plant growth in cultures of cereals, maize, rice and soya. Some of these ethers can also be used for combatting pests of the order acerinae.

CROSS REFERENCE This application is a continuation-in-part of my application, Ser. No. 786,762 filed Dec. 24, 1968, now abandoned.

DETAILED DISCLOSURE The present invention relates to active substances for compositions for controlling undesirable plant growth in cultures of useful plants, such as cereals, maize, rice and soya and some of these compounds are also useful for combatting pests of the order acarinae (mites, ticks etc.).

The active substances are compounds of the Formula I wherein R is a lower alkyl radical, with 1 to 4 carbon atoms, which is unsubstituted or substituted by a chlorine atom, a phenyl radical that is unsubstituted or mono to trisubstituted by members of the group consisting of halogen atoms, methyl, methoxy, trifluoromethyl or nitro groups,

' or R is the benzyl phenylethyl or cyclohexyl radical;

R is a nitro, formyl, methoxycarbonyl or di-lower alkyl sulfamyl radical, wherein the lower alkyl groups have 1 to 4 carbon atoms;

R is a hydrogen or chlorine atom, a lower alkyl, lower alkoxy group with 1 to 4 carbon atoms, the methoxycarbonyl .or di-ethylsulfamyl group and X are identical and represent chlorine, bromine or iodine atoms.

In these definitions under lower alkyl groups With 1 to 4 carbon atoms, the straight chained or branched radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. butyl and tert. butyl are understood.

3,772,385 Patented Nov. 13, 1973 ice The present invention claims the new oxime-ether-car which are necessary for the manufacture of the compounds of Formula I can be manufactured in a simple manner, for example from 3,5-dihalogeno-4-hydroxybenzyldoxime and an appropriately substituted chlorobenzene of formula in alkaline solution.

If these compounds of Formula II are to be converted to esters of General Formula I then, provided the reaction is not too drastic, all usual esterification methods can be applied to the conversion of the phenolic OH group. In order to ensure mild conditions, it is appropriate to start from the phenolate and to react with appropriate carboxylic acid halides. It is also possible to produce the phenylester grouping at temperatures in the range of 0 to C. with carboxylic acids or carboxylic acid anhydrides, with acid esters or lactones or in individual cases also with ketenes.

For converting the starting products H to the corresponding carbamates, the phenolic OH group can be reacted according to usual methods with isocyanates of the type or with compounds which can transiently form these isocyanates, or also with carbamic acid chlorides of the type It is however also possible first to manufacture the corresponding phenolchlorocarbonate from the OH group by means of COC1 and then to allow this, where possible, to react with an amine R NH or R NHCH R in each case has the significance given for Formula I. Possible solvents are generally acetonitrile, ether, dioxane, dimethylformamide, dimethylsulphoxide and others.

The herbicidal selectivity in varieties of grain, maize and rice on the one hand and in leguminosae (peas, beans, soya beans, clover and lucerne) on the other, on postemergent treatment, follows for all compounds of Formula I from the field of use initially quoted, though to diiferent extents. Particularly outstanding representatives are those or of the type of general Formula III x R1-NH-C o-0-oH=N-0-Ar X (III) wherein R and X have the significance given initially and Ar especially represents the following substituted phenyl groups:

COOCHa Alkyl O-Alkyl Alkyl In the formulae quoted alkyl is intended to represent lower, including branched alkyl residues having at most 4 C atoms.

The new oxime-ether-carbamates can be used alone or mixed with other pesticides or biologically stimulating or inhibiting substances or with solid carriers, solvents, diluents, thickeners, dispersing agents, wetting agents or adhesives or optionally with the addition of fertilisers.

Depending on the end use, the new subtsnces can be used as pesticides in various ways such as form part of the state of the art and are for example described in U.S. Pat.

3,329,702 or British Pat. 1,047,644 or Swiss Pat. 424,359.

In many cases it is advantageous to use granules to achieve uniform release of active substances over a longer period of time. These granules can for example be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granulated material, for example Attapulgite or SiO and removing the solvent.

In the form of one or other use such materials can also be applied by distribution over large areas (spraying, dusting and the like) by means of aircraft.

The various use forms of such materials can be more closely suited to the end uses in the usual manner by adding substances which improve the distribution, adhesion, rain resistance and possibly the penetrating power, such as for example fatty acids, resins, wetting agents, glue, caseine or alginates.

In the manufacture of herbicidally active materials there are furthermore numerous possible components or use in combinations, of which the most important representatives are quoted below:

N phenyl N, N dimethylurea, N-p-chlorophenyl- N, N dimethylurea, N 3,4 dichlorophenyl-N,-N'- dimethylurea, N 3,4 dichlorophenyl-N'-methoxy-N'- methylurea, N 4 bromo 3 chlorophenyl-N-methoxy- N methylurea, trichloracetic acid, 2,6-dichlorobenzonitrile, 2,3,6 trichlorobenzoic acid, 2,4-D, 2,4,5-T, MCPB, MCPP, isopropyl-carbanilate, isopropyl-3-chlorocarbanilate, N 3 chlorophenylcarbamic acid 4'-chlorobutin 2 yl 1 ester, 2,3,6-trichlorophenylacetic acid and salts, 2 chlorodiallylacetamide, 2-chloro-4,6-bisethylamino s triazine, 2 methoxy 4,6 bis-ethylamino s triazine, 2 azido 4 methyl-thio-6-isopropylaminotriazine, the monomethylarsenate di-Na, salt, various arsenites, Na metaborate, Na chlorate and sulphamic acid.

When using the materials against ectoparasites on farm animals such as cattle, sheep, goats and others, it is advantageous to use dipping baths in which the active substances are present alone or, as described, in an emulsified or dispersed form.

In the following text the parts denote parts by weight.

EXAMPLE 1 are obtained in an analogous manner.

[Compound 36] TABLEContinued TABLEContinued Melting point, C. Melting point, 0. R1 (decomposition) R1 (decomposition) CFa 5 CH3 In a similar manner the compound of formula 65 Br 166-190 B1 5 N09 CE; 66 C Fa 178-181 /NCOO CH=NO N0a Q CH: Br

c1 Melting po1nt 158-160 [decomposition] 3r 0 l is obtained by reacting the Na salt of 3,5-dibromo-4-hy- C1 droxybenzaldoxime O-2',4 dinitrophenyl ether with dimethylcarbamoyl chloride.

The following compounds of the type of The following compounds of the type of I NO:

131' I110: R1NHC 0-0 CH=NO NO:

R1-NHCOO -CH=NO CH0 1 are obtained in an analogous manner are obtained in an analogous manner to that which has been described for the manufacture of compound 36.

Melting point, 0. R1 (decomposition) Melting point, C. R 68 CH- 198-199 1 (decomposltion) 69-" C2E5 180481 Compound No.:

CH 9669 CF; 182-184 55 207-208 6 Cl 197-199 5 72 Cl 175-176 The following compounds are obtained in an analogous The following compounds of the type of manner are obtained in an analogous manner l Melting point 124-126 C. [decomposition] No. 76 Melting point, C.

I IEIO a l R1 (decomposition) Compound No.: CHa-NH-C O-O --CH=N-0 N02 86 CH? g 210 I CH3 87 CICH OHz- 206207 20 Cl 187-189 Melting point 173-174 C. [decomposition] The following compounds of the type of 89 c F, 186-18 1 9 R1NHC O-0CH=NOQ NW O o MQ- 191 193 C1 C1 91 J1 187-189 are obtained in an analogous manner Q- Melting point C. R1 (demmpmmm) The following compounds of the type of Compound N 0.

0113- 185-188 7s- ClCHr-C'Hr 180-182 C1 N02 l /CH3 79 174-177 R1-NH-C0-O-CH=NOSOz-N\ are obtained in an analogous manner 82 132-184 Melting point, C.

F z R (decomposition) s3 F30 176-173 (Impound The following compounds of the type of n-Propyl are obtained in an analogous manner Melting point, C.

Melting point, C.

R1 (decomposition) R1 (decomposition) Compound N 0.: 187-188 5 s- Cl-CHPCHP 189-190 107- CaH5- 184-185 173-174 108 Cl 183-184 1 10 The following compounds of the type of 110 CH 177-178 C1 IIQOQ 111- F10 163-164 al-mi-oo-o -CH=N-ON0z l 1 C1 N(CH1)2 are obtained in an analogous manner 01 179480 Melting point, C. The following compounds of the type of R1 (decomposition) Br N02 Compound N 0.: l

97 CH;- 182-188 98 (ll-CHPCHP 170-172 R1NH-OO-O CH=N-O -00 0 CH;

are obtained in an analogous manner 100 Cl 173-174 Melting point, C. Cl R1 (decomposition) Compound No.: 101 CF 162463 113 165-167 115 Cl 165-166 I The following compounds of the type of 110 CF; 168-170 i OH I lh-NH-CO-O CH=NOY -SOzN\ Cl are obtained m an analogous manner The following compounds of the type of Melting point, C. R1 (decomposition) Br 1Y0 Compound No.:

102 CHP 192493 1 N H C 0 Q N 0 N01 103 180-182 Br 0 0 0 on;

are obtained in an analogous manner 04 C1 183 184 Melting point, C.

x (decomposition) 5 Compound No.: 10 G1 179 181 11s 011 181-182 119 Cl-CHz-CHz- 148-149. 5 C1 05 (:1 -166 The following compounds of the type of 121 Q 178-179 (0 Br N02 122 Cl 161-163 R1NHCO0CH=N0 NO4 Br 0 Cl Examples of formulations Dusting agents. Equal parts of an active substance according tothe invention and of precipitated silica are finely ground. Dusting agents which preferably contain 1-6% of active substance can be manufactured therefrom by mixing with kaolin or talc.

Spraying powders.-In order to manufacture a spraying powder the following components are for example mixed and finely ground: 50 parts of active substance according to the present invention, 20 parts of Hisil (highly adsorptive silica), 25 parts of bolus alba (kaolin), 3.5

'parts of a reaction product of p-tert.octylpheno1 and ethylene oxide and 1.5 parts of sodium 1-benzyl-2-stearyllbenzimidazole-6,3-disulphonate.

Compound No Ipomoea. Daucus- Emulsion concentrate.Easily soluble active substances can also be formulated as an emulsion concentrate in accordance with the following instructions: 20 parts of active substance, 70 parts of xylene and 10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzene-sulphonate are mixed. On dilution with water to the desired concentration a sprayable emulsion results.

EXAMPLE 3 Selective herbicidal action The compounds encompassed by Formula I show a good action in combatting dicotyledon plants in the post-emergent treatments.

The treatment of the experimental field with active substances according to the invention is carried out 12 days after sowing, when the plants have developed one to two new leaves after emerging. The amounts used are 2, l and 0.5 kg. of active substance per hectare.

The results are presented in the three tables which follow. As shown by the results, the compounds mentioned are throughout suitable for combatting dicotyledon plants in varieties of grain. Wheat, barley, oats and maize are completely spared by almost all compounds. Some compounds are tolerated by soya and flax cultures. The compounds 27, 33, 3s, 3s, 39, 40, 49, 72, 73, 113, 114, 116 and 118 are tolerated by rice. The active substances 89 and 91 only affect rice plants slightly but destroy the well-known rice weed Panicum.

The following ratings are applicable to the assessment in the tables: 1-2=no action, 3-4=s1ight damage, 5-7= severe damage and 8-9=plant died.

TABLE 1 Norm-Use amounts: 1 kg. of active substance/hectare.

Improvement..-

Variety of plant:

Triticum...-

Hordeum- Alopeeuru TABLE 1A Cyperus veg Oynodon veg Gossypium--- Amaranthus N own-Use amounts: 1 kg. of active substance/hectare.

mar tal-06 06000 h t- HHi-n- HHt-n-n-u ocomwgaomnoncnqco HHHHFIHI-IHHHHQ-I cowummra concmo HHHHNNH-IDH-IHHH 17 For comparative purposes the results obtained in this test with previously known substances with partly similar chemical structure are shown in Table II.

The compounds thus tested are known from the French Patent No. 1,494,078

Cl- NH-O O OCH:

methyl-3,4-dichloro-carbanilate known from the U.S. Pat. No. 3,116,995 and NH-COO CH(CH3)1 isopropyl-N-(3-chlorophenyl)carbamate, known under the trade name CIPC.

Compound A B C Amount applied in kg./ha.

Variety of plant:

' ticum Oyperus veg. Cynodon veg-- Gossypium.-...- Amaranthus.

una wcoccthce en-no wwcaggco wqeo (DMNND clwamh HNQNFWUMF EXAMPLE 4 Several compounds of the present application were compared in a field test with the compound 50% of one of the active compounds to be tested 33.5% of bolus alga (kaolin) 11% of the ammonium salt of ligninsulfonic acid 4.5% of sodium dinaphtylmethanedisulfonate (product commercially available under the trade name Neradol) 18 The assessment of the test was made 4 weeks after the treatment and the plants were evaluated according to the following key:

Note Crop Weed 5 1 (optimum)- No damage, as control... Plants killed.

2-4- Slight coverable damage Heavy damage.

Heavy irreversible damage Shdght recoverable amage. 9- Plant kill No damage, same as untreated control.

10 I I I The results are given 1n the followmg table. One note is given for the crop, another for the evaluation of the weeds in that particular lot in general and a third one for the problem weed in each individual lot.

Compound tested Concentration applied in kg.ll1a 1 2 1 2 1 2 1 2 1 2 1 2 Crop: soya 6 4 5 4 3 4 Weedsin general"... 6 3 6 5 4 3 Crop: winterwheat 1 1 1 2 1 1 Weeds in general"-.- 6 3 4 4 Veronica arumsis 9 2 6 1 2 2 In these field tests, in post emergence application of 1 and/or 2 kg. per hectare, the compounds of the present application show selective herbicidal activity in crops of soya and excellent selective herbicidal activity in crops of summer and winter wheat.

The compound A according to the French Pat. No. 1,494,231 shows in the same tests no selective herbicidal activity in soya and though it is very compatible towards wheat, its weed controlling ability -is not satisfactory.

EXAMPLE 5 In order to test the acaricidal action, phaseolus plants in the two-leaf stage are infested, 12 hours before the treatment, by placing pieces of leaf attacked by spinning mites on them. After 12 hours a population in all stages of development is present on the test plant.

The active substance No. 75 was sprayed in the form of an emulsion onto the plant through a fine atomiser in such a way that a uniform deposit of droplets was produced on the surface of the leaf. After 7 days the mortality was determined and expressed as a percentage. The following mortality values were determined for two varieties of spinning mite after 2 and 7 days:

(a) Tetranychus urticae R is a lower alkyl radical, with 1 to 4 carbon atoms,

which is unsubstituted or substituted by a chlorine atom,

a phenyl radical that is unsubstituted or mono to trisubstituted by members of the group consisting of halogen atoms, methyl, methoxy, trifluoromethyl or nitro groups, or R is the benzyl phenylethyl or cyclohexyl radical;

R is 9. nitro, formyl, methoxycarbonyl or di-lower alkyl sulfamyl radical, wherein the lower alkyl groups have 1 to 4 carbon atoms;

R is a hydrogen or chlorine atom, a lower alkyl, lower alkoxy group with l to 4 carbon atoms, the methoxycarbonyl or di-methylsulfamyl group and X are identical and represent chlorine, bromine or iodine atoms. 2. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

3. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

4. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

5. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

6. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

7. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

8. Compounds according to claim 1 of formula 9. Compounds according to claim 1 of formula wherein R and X have the meaning given in claim 1. 10. Compounds according to claim 1 of formula wherein R has the meaning given in claim 1.

11. Compounds according to claim 1 of the formula wherein R has the meaning given in claim 1.

12. Compounds according to claim 1 of the formula COOCH:

wherein R has the meaning given in claim 1.

13. The compound according to claim 3 of the formula References Cited UNITED STATES PATENTS 3,492,333 1/1970 Pickore et a1. 260-472 LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, Assistant Examiner UNITED STATES PATENT oFFmE CERTIFICATE OF CORRECTION Patent No. 772,385 Dated November 13, 1973 @Ifiventortst Adolf Hubele It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 20} 8, line 6, after the formula insert the following:

whereinR has the meaning given in claim 1 Signed and sealed this 11th day of February '1975.

(SEAL) Attes't:

r C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks FORM PC3-1050 (10 59) v usco g37 .pQ I 1 i ".5. GOVERNMENT PRINTING OFIICI 2 I". O-SIG'SSI,

1 Patent n 3,772,385

, nventofls) Adolf Hubele UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated November 13, 1973 It is certified thaterror appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

The following should be inserted in the heading:

Claims priority, application Switzerland January 5,. 1968, No. 121/68 Signed and sealed this 16th day of July 1974.

:- (SEAL) Attest:

MCCOY M. GIBSON, JR. Attesting Officer C. MARSHALL DANN Commissioner of Patents FORM Pep-10$) (10-69) uscoMM-Dc BD376-P69 W "is. GOVERNMENT PRINTING OFFICE I989 0-356-534. 

